US20170320247A1 - Composite of metal member and resin mold, and metal member for formation of composite with resin mold - Google Patents

Composite of metal member and resin mold, and metal member for formation of composite with resin mold Download PDF

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Publication number
US20170320247A1
US20170320247A1 US15/656,679 US201715656679A US2017320247A1 US 20170320247 A1 US20170320247 A1 US 20170320247A1 US 201715656679 A US201715656679 A US 201715656679A US 2017320247 A1 US2017320247 A1 US 2017320247A1
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United States
Prior art keywords
resin mold
metal member
composite
roughened
roughened portion
Prior art date
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Abandoned
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US15/656,679
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English (en)
Inventor
Hideki Aizawa
Shouji KOIZUMI
Michio Ookubo
Kunio Shibata
Makoto Hashimoto
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Furukawa Electric Co Ltd
Furukawa Precision Engineering Co Ltd
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Furukawa Electric Co Ltd
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Assigned to FURUKAWA ELECTRIC CO., LTD., FURUKAWA PRECISION ENGINEERING CO., LTD. reassignment FURUKAWA ELECTRIC CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AIZAWA, HIDEKI, KOIZUMI, SHOUJI, OOKUBO, MICHIO, HASHIMOTO, MAKOTO, SHIBATA, KUNIO
Assigned to FURUKAWA ELECTRIC CO., LTD. reassignment FURUKAWA ELECTRIC CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FURUKAWA PRECISION ENGINEERING CO., LTD.
Publication of US20170320247A1 publication Critical patent/US20170320247A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4821—Flat leads, e.g. lead frames with or without insulating supports
    • H01L21/4828—Etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/565—Moulds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • H01L23/3142—Sealing arrangements between parts, e.g. adhesion promotors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49541—Geometry of the lead-frame
    • H01L23/49548—Cross section geometry
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/50—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor for integrated circuit devices, e.g. power bus, number of leads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0072—Roughness, e.g. anti-slip
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • H01L23/3114—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed the device being a chip scale package, e.g. CSP
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/562—Protection against mechanical damage

Definitions

  • the present disclosure relates to a composite of a metal member and a resin mold to be used for electronic devices, home electric appliances, parts for vehicles, on-vehicle materials, and so on, and a metal member suitable for formation of such a composite.
  • Japanese Laid-Open Patent Publication Nos. 10-294024, 2010-167475, and 2013-111881 each propose a technique to roughen the surface of a metal member to form unevenness particularly in a joint between different materials for enhancement of the adhesion at the joint.
  • the adhesion strength between metal and resin is insufficient particularly at high temperatures, and molecules of water vapor clusters or the like may permeate the joint interface between metal and resin to deteriorate a functional part in the inside.
  • the present disclosure is related to providing a composite of a metal member and a resin mold, the composite achieving excellent adhesion between metal and resin and being capable of exerting high airtightness even in use under a high-temperature environment, and a metal member suitable for formation of such a composite.
  • the present inventors diligently studied, and found that a composite of a metal member and a resin mold in which the metal member has a roughened portion in a joint to the resin mold in the surface, and in a specific interface region including a joint interface between the roughened portion and the resin mold, a void between the roughened portion and the resin mold has a specific average volume in a unit area and a specific maximum dimension achieves excellent adhesion between metal and resin and is capable of exerting high airtightness even in use under a high-temperature environment, and thus completed the present disclosure.
  • a composite including a metal member and a resin mold formed jointed to a surface of the metal member, wherein
  • the present inventors succeeded in providing a composite of a metal member and a resin mold, the composite achieving excellent adhesion between metal and resin and being capable of exerting high airtightness even in use under a high-temperature environment, and a metal member suitable for formation of such a composite.
  • FIG. 1 is a schematic perspective view of a composite of a metal member and a resin mold according to the present disclosure.
  • FIG. 2 is a schematic view illustrating the I-I cross-section (X-Y plane) of the composite in FIG. 1 .
  • FIG. 3A is a schematic view illustrating the II-II cross-section (X-Z plane) of the composite in FIG. 1
  • FIG. 3B is an enlarged schematic view illustrating a part around a joint between a metal member and a resin mold, where the part is enclosed by a frame in dash-dot lines in FIG. 3A .
  • FIG. 4 is an enlarged schematic perspective view of the metal member illustrating a part around the joint to the resin mold as an extracted view only of the metal member constituting the composite in FIG. 1 .
  • the composite according to the present disclosure is a composite including a metal member and a resin mold formed on a surface of the metal member, wherein the metal member has a roughened portion in a joint to the resin mold in the surface.
  • FIG. 1 illustrates one embodiment of the composite according to the present disclosure
  • the reference signs 1 , 20 , and 30 in FIG. 1 indicate the composite, a metal member, and a resin mold, respectively.
  • FIG. 2 is the I-I cross-section (X-Y plane) including a surface of the metal member 20 of the composite illustrated in FIG. 1 .
  • the reference sign 40 indicates a surface of the metal member 20 , which is a joint to the resin mold 30 .
  • the composite 1 has a form in which a part of the metal member 20 is embedded in the resin mold 30 , and another part is exposed to the outside of the resin mold 30 . Then, the metal member 20 has a joint 40 to the resin mold 30 in the surface.
  • the joint 40 is a part of the surface of the metal member 20 , and present between a portion embedded in the resin mold 30 , 20 a , and a portion exposed to the outside, 20 b . It follows that the joint 40 corresponds to the portion 40 segmented by dashed lines in a surface of the metal member 20 in FIG. 2 .
  • the form of the composite 1 is not limited to the form illustrated in FIGS. 1 and 2 , and may be, for example, a form in which the resin mold 30 is attached to one surface of the metal member 20 .
  • FIG. 3A is the II-II cross-section (X-Z plane) of the composite 1 illustrated in FIG. 1
  • FIG. 3B is an enlarged view of (B) enclosed by a rectangular frame of dash-dot lines in FIG. 3A
  • the reference signs 21 , 41 , and 43 indicate a roughened portion, a joint interface between roughened portions 21 and the resin mold 30 , and a specific interface region including a joint interface 41 , respectively.
  • the metal member 20 has roughened portions 21 at the joint 40 to the resin mold 30 in the surface.
  • the joint interface 41 is present between the roughened portions 21 of the metal member 20 and the resin mold 30 .
  • a specific region including the joint interface 41 is defined as the specific interface region 43 .
  • the specific interface region 43 is a region formed to include the joint interface 41 and to have thicknesses in the thickness direction (depth direction) from the position of the joint interface 41 to the resin mold 30 and the metal member 20 including the roughened portions 21 , respectively, of approximately 15 ⁇ m (each of the regions represented by the dash-dot-dot lines in FIG. 3B ).
  • the average volume in a unit area of voids between the roughened portions 21 and the resin mold 30 is 0.05 lams or smaller per 1 ⁇ m 2 of a plane generally parallel to the joint interface 41 , and the maximum dimension of the void is 1000 nm or smaller.
  • the plane generally parallel to the joint interface refers to a plane parallel to the smooth surface.
  • Such a plane is also substantially parallel to a surface of the metal member which is present in a plane extended from the joint interface and on which no roughened portions are formed.
  • the average volume in a unit area of voids is a value calculated by dividing the sum total of the volume of voids by the area of a plane generally parallel to the joint interface between the roughened portions of the metal member and the resin mold to convert to the volume of voids present in 1 ⁇ m′ of the plane.
  • the maximum dimension of a void is a maximum value among the longest widths of voids present in the specific interface region. Specific measurement methods for them will be described later in Examples.
  • the composite according to the present disclosure has a closed space in the resin mold, and the closed space includes a metal surface not covered with the resin mold.
  • a closed space allows the composite to incorporate a functional part in the inside.
  • the composite according to the present disclosure further includes a functional part in the resin mold.
  • the functional part is characterized in that it is present in a confined space consisting of the resin mold and the metal member.
  • the surface of the functional part may be closely attached to the resin mold or the metal member, or only a part of the surface may be closely attached to the resin mold or the metal member, or the surface may be closely attached to neither the resin mold nor the metal member.
  • Examples of the functional part include integrated circuits such as microprocessors, microcontrollers, memories, and semiconductor sensors.
  • the metal member may be in any shape, for example, a sheet, a wire, a box, a sphere, a shape obtained by bending any of them, or a shape obtained by jointing several of them.
  • the material of the metal member is not particularly limited, and can be appropriately selected from known metals in accordance with the intended use.
  • Examples of the material of the metal member include metals consisting of one selected from copper, aluminum, iron, titanium, zinc, magnesium, lead, and tin, and alloys containing two or more thereof, and examples of iron alloys include iron-nickel alloy (42 alloy), and stainless steels.
  • a part (e.g., the surface) of the metal member may be plated.
  • the metal member is preferably copper or aluminum.
  • lasers with a wavelength from visible to near-infrared are relatively accessible, and thus widely used.
  • copper and aluminum, each of which has high absorbance at a wavelength from visible to near-infrared, are particularly preferred in that they exhibit good processability in laser processing in the wavelength region.
  • the thickness is preferably 1 ⁇ m to 10 mm, and more preferably 30 ⁇ m to 2 mm. If the generally sheet-shaped metal member is thin, the shape is likely distorted when the metal member is partially provided with roughened portions.
  • the metal member according to the present embodiment has a roughened portion in a joint to the resin mold.
  • This configuration provides good jointing to the resin mold, and high airtightness is achieved when a composite with the resin mold is formed. It is only required that a roughened portion be formed in at least a part of a joint to the resin mold in a surface of the metal member, and a roughened portion may be formed in a part of a joint, or in the whole surface of a joint, or even beyond a joint. From the viewpoint of easiness in treatment after formation of the resin mold (e.g., deburring), it is preferred that no roughened portions be formed in portions not embedded in the resin mold (the portions of the metal member 20 exposed to the outside, 20 b , in FIG. 1 ), and it is preferred that a roughened portion be formed in the whole surface within a joint from the viewpoint of enhancement of the adhesion.
  • the method for forming a roughened portion as described above is not particularly limited, and a known roughening method which enables formation of unevenness in a part of the surface of the metal member is suitably used.
  • known roughening methods include laser irradiation, etching, roughening plating, blasting, and breaking.
  • the roughened portion refers to a portion of the metal member in which the surface geometry has been modified through treatment to form unevenness in a part of the surface of the metal member.
  • the roughened portion is a portion affected by laser irradiation.
  • multiple shots of laser irradiation form a pattern of dotted uneven portions on the metal surface, and thus roughened portions are formed.
  • a region within 100 ⁇ m from the outer periphery of a portion processed with one spot of laser irradiation spot-irradiated portion: dotted uneven portion
  • the metal member further has a roughened region including the roughened portion in a part of the surface.
  • the roughened region refers to a region including a roughened portion. In the case of a region with roughened portions continuously disposed, the roughened region and the roughened portions are the same region.
  • the roughened region is a region surrounding the whole of the roughened portions.
  • the roughened region consists of roughened portions and the other portion (unroughened portion: a portion which has not been roughened).
  • the minimum distance between roughened portions is 1000 ⁇ m or larger, the respective roughened portions shall be included in different roughened regions (see FIG. 5B ).
  • the surface of the metal member preferably consists of a roughened region including the roughened portion and an unroughened region without the roughened portion.
  • the unroughened region refers to a surface of the metal member excluding the roughened region. That is, the unroughened region does not include any roughened portion obtained through roughening and consists only of unroughened portions.
  • the arithmetic average roughness (Ra) of the roughened portion is preferably 0.13 ⁇ m to 100 ⁇ m, and more preferably 0.2 ⁇ m to 10 ⁇ m.
  • the arithmetic average roughness can be calculated from surface geometry data obtained in measurement with a laser microscope in accordance with a method described in an ISO standard (ISO 25178).
  • the surface roughness of the metal member has large impact on the permeability of gas which permeates the joint interface between the resin mold and the metal member. Specifically, in the case of large surface roughness, partial peeling, which is caused by a force applied to the joint interface between resin and metal due to the difference of the coefficient of thermal expansion between the resin mold and the metal member or the pressure difference between the inside and the outside, is generated to a larger extent, which facilitates permeation of gas molecules. In the case that the surface roughness of the metal member is small, on the other hand, such partial peeling is generated to a smaller extent, gas molecules or clusters formed of gas molecules are less likely to permeate. However, sufficient adhesion could not be achieved if the surface roughness is excessively small.
  • the surface roughness of the metal member is preferably 0.13 ⁇ m to 100 ⁇ m, and more preferably 0.2 ⁇ m to 10 ⁇ m, in arithmetic average roughness (Ra).
  • the surface roughness and the arithmetic average roughness as an indicator of the physical property can be appropriately adjusted in accordance with the roughening method or conditions therefor.
  • the abundance ratio of oxygen in the roughened portion is preferably higher than the abundance ratio of oxygen in the unroughened region.
  • the abundance ratio of oxygen in the roughened portion is preferably higher than the abundance ratio of oxygen in the unroughened portion. It follows that, in the case that the roughened region includes few unroughened portions and is substantially the same region as the roughened portion, the abundance ratio of oxygen in the roughened region is substantially identical to the abundance ratio of oxygen in the roughened portion, and the abundance ratio of oxygen in the roughened region becomes lower than the abundance ratio of oxygen in the roughened portion as the roughened region includes a larger number of unroughened portions.
  • the roughened region is a region including a roughened portion, and hence the abundance ratio of oxygen therein is substantially higher than the abundance ratio of oxygen in the unroughened region. Specific measurement method will be described later in Examples.
  • the abundance ratio of oxygen in the roughened portion has large impact on the adhesion between the resin mold and the metal member. Specifically, in the case that the abundance ratio of oxygen in the roughened portion is equivalent to or lower than the abundance ratio of oxygen in the unroughened region, it is expected that a resin molten in formation has low wettability, and a void is more likely to be generated in the interface between metal and resin. In the case that the abundance ratio of oxygen in the roughened portion is higher than the abundance ratio of oxygen in the unroughened region, on the other hand, it is expected that the energy generated when a resin molten in formation is oxidized by oxygen present on the metal surface allows the resin to enter fine portions of the roughened structure, and a void is less likely to be generated in the interface between metal and resin.
  • the abundance ratio of oxygen in the roughened portion is preferably higher than the abundance ratio of oxygen in the unroughened region, and more preferably 1.3 times or more of the abundance ratio of oxygen in the unroughened region.
  • the abundance ratio of oxygen in the roughened portion can be appropriately adjusted in accordance with conditions for formation of the roughened portion (e.g., the roughening method, conditions therefor, formation density of the roughened portion).
  • the roughened portion preferably has a collection of dotted uneven portions.
  • the roughened portion corresponds to a region within 100 ⁇ m from the outer periphery of each of the dotted uneven portions.
  • the method for forming such dotted uneven portions is not particularly limited, and such dotted uneven portions can be formed, for example, through laser irradiation or the like.
  • the depth of each of the dotted uneven portions is preferably 100 nm or more, and more preferably 500 nm or more, from the viewpoint of achievement of sufficient adhesion strength. From the viewpoints of suppression of the strain of the metal part and prevention of deterioration of the metal due to oxidation, the depth of each of the dotted uneven portions is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the density of the dotted uneven portions is preferably 20 to 2000 portions/mm 2 , and more preferably 50 to 1000 portions/mm 2 , from the viewpoints of suppression of the strain of the metal member and prevention of deterioration due to oxidation.
  • the diameter of each of the dotted uneven portions is preferably 200 ⁇ m or smaller, more preferably 100 ⁇ m or smaller, and even more preferably 50 ⁇ m or smaller, from the viewpoint of formation of unevenness with fine geometry.
  • a roughened portion is defined as a region within 100 ⁇ m from the outer periphery of one dotted uneven portion.
  • one roughened portion formed of one dotted uneven portion preferably overlaps with another roughened portion formed of another dotted uneven portion, and more preferably such roughened portions continuously overlap with each other.
  • the airtightness can be ensured more reliably through continuous roughened portions. It is preferred that such roughened portions be present in a roughening pattern in which roughened portions each formed of an independent dotted uneven portion continuously overlap with each other. Specifically, it is more preferred that roughened portions be present in a roughening pattern with dotted uneven portions continuously disposed.
  • the geometry of the roughening pattern is not particularly limited, and examples thereof include zonal patterns and striped patterns.
  • Such a roughening pattern is preferably formed along the joint to the resin mold, and may be formed generally in parallel with the planar boundary with the resin mold formed on the metal member.
  • a functional part is disposed in the inner space of the resin mold, such a roughening pattern is preferably formed such that the roughening pattern at least surrounds the functional part.
  • the minimum value of the width of the roughened region is preferably 200 ⁇ m or larger, and more preferably 500 ⁇ m or larger.
  • the minimum value of the width of the roughened region refers to the length of the roughened region on the line L crossing, in the shortest distance, the joint to the resin mold in the surface of the metal member (the line in the surface of the metal member between the point a in the inside of the resin mold and the point b exposed to the outside of the resin mold, see FIG. 4 ).
  • the length of a part of the line L in which roughened portions are continuously present is preferably 200 ⁇ m or larger, and more preferably 500 ⁇ m or larger.
  • the roughened portion may be present in a plated portion, or may be present in a portion of exposed base, or may be present over a plated portion and a portion of exposed base.
  • a CW (continuous wave) laser or a pulse laser can be used.
  • a pulse laser for example, a collection of dotted uneven portions can be easily formed through formation of a pattern of processed portions on the metal surface by multiple shots of laser irradiation (portions spot-irradiated with a laser). By further combining such collections, a pattern of repeated stripes can be formed.
  • FIG. 4 is an enlarged schematic view illustrating of the joint 40 to the resin mold 30 as an extracted view only of the metal member 20 in the composite 1 in FIG. 1 .
  • the reference signs 22 , 23 , 25 , and 27 indicate an unroughened portion, a roughened region, an unroughened region, and a portion spot-irradiated with a laser, respectively.
  • FIG. 5A is a schematic view especially illustrating the relation between the spot-irradiated portion 27 and the roughened portion 21
  • FIG. 5B is a schematic view especially illustrating the relation among the roughened portions 21 , the unroughened portion 22 , the roughened regions 23 , and the unroughened region 25 .
  • FIG. 6 is a schematic view in the case that roughened portions are formed in a roughening pattern of repeated stripes.
  • a pulse width in the order of 0.1 picoseconds to 1 millisecond can be preferably used from the viewpoint of achievement of the above-described geometry through processing.
  • Energy per pulse of 10 ⁇ J to 1000 ⁇ J can be preferably used.
  • the spot diameter is preferably 200 ⁇ m or smaller, more preferably 100 ⁇ m or smaller, and even more preferably 50 ⁇ m or smaller, from the viewpoints of higher energy density and formation of unevenness with fine geometry. From the viewpoint of condensation of laser light, the spot diameter is preferably 20 ⁇ m or larger.
  • the energy density per spot is preferably 1 to 50 J/cm 2 .
  • the energy density is a value calculated by dividing pulse energy by the area of a spot-irradiated portion. If the energy density is lower than 1 J/cm 2 , processing cannot be performed sufficiently. If the energy density is higher than 50 J/cm 2 , metals molten or broken by laser irradiation are scattered and attached therearound. Since these attached matters lower the bonding force in wire bonding, for example, generation of attached matters is not preferred.
  • a wavelength of 300 nm to 20000 nm can be preferably used.
  • the arithmetic average roughness and oxygen concentration of the roughened portion can be appropriately adjusted in accordance with the roughening method, and can be appropriately adjusted, for example, through adjustment of the laser output, spot diameter, spot distribution including spot intervals (p, q in FIG. 4 ), and so on, in laser irradiation.
  • the resin mold according to the present embodiment is a member of a resin material formed at least in a part of the surface of the metal member.
  • thermoplastic resins include polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile/styrene resin (AS), acrylonitrile/butadiene/styrene resin (ABS), methacrylic resin (PMMA), and polyvinyl chloride (PVC).
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • AS acrylonitrile/styrene resin
  • ABS acrylonitrile/butadiene/styrene resin
  • PMMA methacrylic resin
  • PVC polyvinyl chloride
  • thermoplastic resins examples include polyamide (PA), polyacetal (POM), ultra-high-molecular-weight polyethylene (UHPE), polybutylene terephthalate (PBT), GF-reinforced polyethylene terephthalate (GF-PET), polymethylpentene (TPX), polycarbonate (PC), and modified polyphenylene ether (PPE).
  • PA polyamide
  • POM polyacetal
  • UHPE ultra-high-molecular-weight polyethylene
  • PBT polybutylene terephthalate
  • GF-PET GF-reinforced polyethylene terephthalate
  • TPX polymethylpentene
  • PC polycarbonate
  • PPE modified polyphenylene ether
  • thermoplastic resins examples include polyphenylene sulfide (PPS), polyether ether ketone (PEEK), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyethersulfone (PES), and polyamideimide (PAT).
  • PPS polyphenylene sulfide
  • PEEK polyether ether ketone
  • LCP liquid crystal polymer
  • PTFE polytetrafluoroethylene
  • PEI polyetherimide
  • PAR polyarylate
  • PSF polysulfone
  • PES polyethersulfone
  • PAT polyamideimide
  • thermosetting resins examples include phenolic resin, urea resins, melamine resins, unsaturated polyester, alkyd resins, epoxy resins, and diallyl phthalate.
  • elastomers include thermoplastic elastomers and rubbers such as styrene-butadiene rubbers, polyolefin rubbers, urethane rubbers, polyester rubbers, polyamide rubbers, 1,2-polybutadiene, polyvinyl chloride rubbers, and ionomers.
  • thermoplastic resin thermosetting resin, or thermoplastic elastomer
  • a known fibrous filler can be blended.
  • known fibrous fillers include carbon fibers, inorganic fibers, metal fibers, and organic fibers.
  • metal fibers examples include fibers formed of stainless steel, aluminum, copper, or the like.
  • the composite according to the present disclosure is excellent in adhesion between the resin mold and the metal member, and thus can be suitably used for applications requiring retention of an airtight state in the inside or applications requiring adhesion between the metal member and the resin mold.
  • the composite according to the present disclosure is suitable for a composite molded body including an electric/electronic part susceptible to humidity or moisture in the inside.
  • the composite according to the present disclosure is preferably used as a part of an electric or electronic device which may break down by the intrusion of moisture or humidity and for which use in a field requiring waterproofness at a high level, such as a river, a pool, a ski resort, and a bath, is contemplated.
  • the composite according to the present disclosure is useful for housings for electric/electronic devices including a boss made of resin and a holding member in the inside.
  • housings for electric/electronic devices include, in addition to housings for a cell phone, housings for a portable video electronic device such as a camera, a video-integrated camera, and a digital camera; housings for a portable information terminal or communication terminal such as a laptop computer, a pocket computer, a calculator, an electronic diary, a PDC, and a PHS; housings for a portable acoustic electronic device such as an MD, a headphone stereo cassette player, and a radio; and housings for a home electric appliance such as a liquid crystal TV/monitor, a telephone, a facsimile, and a hand scanner.
  • the composite according to the present disclosure is excellent in adhesion in use under a high-temperature environment, and thus can be preferably used for a part or the like to be used under a high-temperature environment. Examples
  • a copper sheet of 20 mm ⁇ 70 mm ⁇ 2 mm was prepared, and roughened portions were formed on the surface of the copper sheet with a laser.
  • the conditions for laser irradiation were as follows.
  • an MD-V9600A manufactured by KEYENCE CORPORATION
  • the spot diameter and spot interval p were as shown in Table 1, and the spot interval q was set at 200 ⁇ m, the number of spot lines was set at three (the pattern illustrated in FIG. 4 ), and the width of the roughened region was set at 630 ⁇ m.
  • the spot intervals (p, q) are in accordance with those in FIG. 4 . Specifically, the spot intervals (p, q) are each the direct distance between the centers of spot-irradiated portions adjacent to each other.
  • the positions at which roughened portions were formed were set within an area for a joint to a resin mold, as illustrated in FIG. 4 .
  • the arithmetic average roughness (Ra) according to an ISO standard (ISO 25178) was measured for the roughened portions formed on the surface of the metal member.
  • a magnification of 1000 ⁇ and a cutoff value of 80 ⁇ m were used for the conditions for measurement with the laser microscope, and measurement was performed for a rectangle area of 500 ⁇ m ⁇ 350 ⁇ m.
  • the abundance of oxygen element in a region from the metal surface to the depth of 10 ⁇ m was evaluated by using an electron probe microanalyzer (EPMA).
  • EPMA electron probe microanalyzer
  • JXA8800RL manufactured by JEOL Ltd.
  • an area in which the arithmetic average roughness was within 0.10 ⁇ m to 100 ⁇ m was selected for measurement from around the joint between the metal member and the resin mold for each of the composites in Examples and Comparative Examples, and cut out with an FIB to reveal a cross-section perpendicular to the joint interface between the resin mold and the metal member as illustrated in FIGS. 3A and 3B .
  • mapping of the intensity of the O-K ⁇ line was performed at an accelerating voltage of 15 kV for an area of 100 ⁇ m square of the roughened portions in the revealed cross-section such that a region from the metal surface to the depth of 10 ⁇ m of the metal member was included. From the resulting mapping data, the average value of the intensity of the O-K ⁇ line in the region from the metal surface to the depth of 10 ⁇ m of the metal member was calculated.
  • (3) (2) was performed for 10 arbitrarily selected sites including a roughened portion, and the average value of the intensity of the O-K ⁇ line was calculated for each of the 10 sites.
  • each of the composites in Examples and Comparative Examples was punctured and a tube was inserted from the hole, and the inside of the composite was pressurized with compressed air at 100 kPa, and pressure loss after 1 minute was measured.
  • the measurement was performed under two types of environments: at normal temperature and at high temperature (60° C.).
  • a pressure loss value of 750 Pa or lower was rated as good, and 500 Pa or lower was rated as particularly good at normal temperature. At high temperature (60° C.), 1500 Pa or lower was rated as good, and 1000 Pa or lower was rated as particularly good.
  • Example 8 to 13 a composite was produced and evaluated in the same manner as in Example 1 except that the material of the metal member, the type of a resin, the spot intervals (p, q), the number of spot lines, and the width of the roughened region were changed as shown in Table 2. The conditions and evaluation results are shown in Tables 2 and 3. In Tables 2 and 3, Example 1 is the same as that shown in Table 1.
  • copper, aluminum, PA, and PBT indicate the above copper sheet, an aluminum sheet of 20 mm ⁇ 70 mm ⁇ 2 mm, the above polyamide resin, and a polybutylene terephthalate resin (1101G-X54, manufactured by Toray Industries, Inc.), respectively.
  • the spot depth, the spot density, and the presence or absence of strain and scattered debris were checked for the copper sheet on which roughened portions were formed.
  • the spot depth depth of unevenness
  • the spot density was the number of spots counted per unit area (mm 2 ).
  • the presence or absence of strain was determined through visual observation around the roughened portions, and the presence or absence of scattered debris was determined through optical microscopic observation particularly around the laser spots.

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  • Engineering & Computer Science (AREA)
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  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Geometry (AREA)
  • Optics & Photonics (AREA)
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  • Injection Moulding Of Plastics Or The Like (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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